Immersion exposure process-use resist protection film forming material, composite film, and resist pattern forming method

ABSTRACT

Provided are a material for forming a resist protecting film which is for use in a liquid immersion lithography process and which is formed on a resist film, wherein the material has the following properties of: being transparent with respect to exposure light; having substantially no compatibility with a liquid for liquid immersion lithography; and causing no mixing with the resist film, a composite film comprising a protective film formed from the material and a resist film, and a method for forming a resist pattern using them. These can prevent both the resist film and the liquid used from changing in properties during the liquid immersion lithography, so that a resist pattern with high resolution can be formed using the liquid immersion lithography.

TECHNICAL FIELD

The present invention relates to a material for forming a resistprotecting film which is advantageously used in a liquid immersionlithography process, especially in a liquid immersion lithographyprocess of the construction in which a resist film is exposed withlithographic exposure light through a liquid present at least on theresist film in a path of the exposure light toward the resist filmwherein the liquid has a predetermined thickness and has a refractiveindex higher than that of air and lower than that of the resist film,thus improving the resolution of a resist pattern. The present inventionalso relates to a resist film having thereon a protective film formedfrom the material for forming a protecting film, and to a method forforming a resist pattern using the protective film.

BACKGROUND ART

In the fabrication of a variety of electronic devices withmicrostructures, such as semiconductor devices and liquid crystaldevices, a lithography method is widely used, and, as the devicestructures are miniaturized, resist patterns in the lithography processare desired to be miniaturized.

Currently, in a state-of-the-art lithography technique, a fine resistpattern having a line width as small as, for example, 90 nm can beformed by the lithography method, and the formation of a further finerpattern will be needed in the future.

A first point for achieving the formation of such a fine pattern that issmaller than 90 nm, is to develop an improved exposure system and acorresponding resist. The point of the development of the improvedexposure system generally includes provision of a light source, such asan F₂ laser, an EUV (extreme ultraviolet light), an electron beam, or anX-ray, a soft X-ray, with a shorter wavelength and of a lens having anincreased numerical aperture (NA).

However, the light source having a shorter wavelength has a problem inthat it requires a new expensive exposure system, and the increase of NAhas a problem in that since there is a trade-off between the resolutionand the depth of focus, the increase in the resolution lowers the depthof focus.

Recently, as a lithography technique which can solve the problems, aliquid immersion lithography method has been reported (cf., for example,Literature 1 (J. Vac. Sci. Technol. B(1999) 17(6), p3306-3309),Literature 2 (J. Vac. Sci. Technol. B(2001) 19(6), p2353-2356, andLiterature 3 (Proceedings of SPIE Vol. 4691 (2002), p459-465). In thismethod, a resist film is exposed through a liquid refractive indexmedium (refractive index liquid, immersion liquid), such as pure wateror a fluorocarbon inert liquid, having a predetermined thickness, withthe liquid refractive index medium lying at least on the resist filmbetween a lens and the resist film on a substrate. In this method, thespace of the path of exposure light, which has conventionally beenfilled with an inert gas, such as air or nitrogen gas, is replaced by aliquid having a larger refractive index (n), for example, pure water,with the result that even though a light source having a wavelength forthe exposure conventionally used is employed, high resolution can beachieved without lowering the depth of focus like the case where a lightsource having a shorter wavelength or a lens having a higher NA is used.

By employing the liquid immersion lithography, a resist pattern having ahigher resolution and an excellent depth of focus can be formed at a lowcost using a lens mounted on the existing exposure system, so that theliquid immersion lithography has attracted a considerable attention.

However, in the liquid immersion lithography process, the resist film isdirectly in contact with the refractive index liquid (immersion liquid)during the exposure, and hence the resist film is vulnerable to invasionby the liquid. Therefore, it is necessary to check whether the resistcomposition conventionally used can be applied as is to the liquidimmersion lithography process.

The resist composition currently commonly used are establishedcompositions that were obtained as a result of examination of a widevariety of candidate resins in respect of the transparency to theexposure light, which is the most essential property to the resistcompositions. The inventors of the present invention have madeexperiments and studies with a view to obtaining from the currentlyproposed resist compositions a resist composition having propertiessuitable for the liquid immersion lithography as such or after slightlyadjusting the formulation of the resist composition. As a result, it hasbeen found that a promising resist composition from a practical point ofview is present. On the other hand, it has been confirmed that there area number of resist compositions which cannot achieve satisfactoryresolution of pattern in the liquid immersion lithography due to achange in their properties by the liquid, but which exhibit fine andhigh resolution in ordinary lithography employing the exposure through alayer of air. Such resist compositions have been established by spendingconsiderable resources on the development, and are excellent in variousresist properties, such as transparency to the exposure light,development properties, and storage stability. These resist compositionsinclude a number of compositions which are poor only in the resistanceto the immersion liquid. Some examples of the compositions, which arenot suitable for the liquid immersion lithography but achieve highresolution in the lithography through a layer of air, are shown in theComparative Examples of the present invention described later.

It has also been confirmed that, even when the resist film suitable forthe liquid immersion lithography is used in the liquid immersionlithography, the quality and non-defective yield are slightly poor, ascompared to those obtained in the exposure through a layer of air.

The suitability for liquid immersion lithography of the conventionalresist film was evaluated based on the following analysis on the liquidimmersion lithography process.

Specifically, for evaluating the performance of formation of a resistpattern by the liquid immersion lithography, it is considered to benecessary and sufficient to confirm three points, i.e., (i) theperformance of the optical system in the liquid immersion lithographyprocess, (ii) the effect of the resist film on the immersion liquid, and(iii) the change of properties of the resist film due to the immersionliquid.

With respect to the performance of the optical system in (i), as isapparent from the case where for example, a photographic sensitive platehaving a surface resistance to water is immersed in water and thesurface of the plate is irradiated with a pattern light, there will beno problem in principle if no light transmission loss, such asreflection, occurs at the water surface and the interface between thewater and the surface of the sensitive plate. The light transmissionloss in this case can be easily removed by optimizing the angle ofincidence of the exposure light. Thus, it is considered that any objectsof the exposure, for example, a resist film, a photographic sensitiveplate, and an image screen, cause no change in the performance of theoptical system, so far as they are inert to the immersion liquid,namely, they are not affected by the immersion liquid, and they do notaffect the immersion liquid. Therefore, a check test for this point isnot required.

The effect of the resist film on the immersion liquid in (ii)specifically indicates that the component of the resist film isdissolved in the immersion liquid to change the refractive index of theliquid. Theoretically, when the refractive index of the immersion liquidchanges, the optical resolution of the pattern exposure is sure tochange, and experiments are unnecessary. It is enough to simply checkwhether the component of the resist film immersed in a liquid isdissolved in the liquid to change the formulation or refractive index ofthe immersion liquid, and it is unnecessary to check the resolution byactual irradiation of a pattern light and development.

Conversely, when the resist film immersed in the liquid is irradiatedwith a pattern light and developed to check the resolution, it ispossible to know as to whether the resolution is excellent or poor.However, it is difficult to judge whether the resolution is affected bythe change of properties of the immersion liquid or the change ofproperties of the resist material or both.

With respect to the phenomenon in which the resolution is lowered by thechange of properties of the resist film due to the immersion liquid in(iii), an evaluation test such that “the resist film after the exposureis showered with the immersion liquid and then developed, and theresultant resist pattern is examined in respect of the resolution” issatisfactory. In this evaluation method, the resist film is directlyshowered with the liquid, and hence the conditions for immersion arevery stringent. In this point, in the test in which the resist filmcompletely immersed in the liquid is exposed, it is difficult to judgewhether the resolution is changed by the change of properties of theimmersion liquid, the change of properties of the resist composition dueto the immersion liquid, or both.

The phenomena (ii) and (iii) above are two sides of the same coin, andcan be grasped by merely checking the change of properties of the resistfilm due to the liquid.

Based on the results of the analysis, the suitability for liquidimmersion lithography of the resist film currently proposed wasevaluated by an evaluation test such that “the resist film after theexposure is showered with the immersion liquid and then developed, andthe resultant resist pattern is examined in respect of the resolution”.The suitability can also be evaluated by simulating the practicalproduction process using a “two-beam interferometry exposure method”that includes using an interfered light caused by a prism as a patternlight for exposure and subjecting a sample immersed in a liquid toexposure.

As mentioned above, for producing a new resist film suitable for theliquid immersion lithography, a large investment of resources for thedevelopment is surely needed. On the other hand, it has been confirmedthat resist compositions having qualities slightly lowered but havingproperties suitable for the liquid immersion lithography are obtainedfrom the currently proposed resist compositions by using the resincompositions as such or by adjusting the formulation of the resincompositions. It has also been confirmed that there are a number ofresist films which cannot achieve satisfactory resolution of pattern inthe liquid immersion lithography due to the change of properties by theimmersion liquid, but which exhibit fine and high resolution in ordinarylithography employing the exposure through a layer of air.

DISCLOSURE OF THE INVENTION

The present invention has been achieved in view of the above problemsaccompanying the conventional technique, and an object of the inventionis to provide a technique for applying a resist film obtained from theconventional resist composition established by spending considerableresources on the development to the liquid immersion lithography.Specifically, an object the invention is to provide a specificprotective film temporarily formed on the surface of a conventionalresist film, thus making it possible not only to prevent both the resistfilm and the liquid used from changing in properties during the liquidimmersion lithography but also to form a resist pattern with highresolution using the liquid immersion lithography.

For solving the above problems, the material for forming a resistprotecting film for use in a liquid immersion lithography process of thepresent invention is a material for forming a resist protecting filmwhich is for use in a liquid immersion lithography process and which isformed on a resist film, wherein the material has the followingproperties of: being transparent with respect to exposure light; havingsubstantially no compatibility with a liquid for liquid immersionlithography; and causing no mixing with the resist film.

The composite film for use in a liquid immersion lithography process ofthe present invention comprises a protective film and a resist film,wherein the protective film has the following properties of: beingtransparent with respect to exposure light; having substantially nocompatibility with a liquid for liquid immersion lithography; andcausing no mixing with the resist film, and wherein the protective filmis formed on the surface of the resist film.

The method for forming a resist pattern of the present invention is amethod for forming a resist pattern using a liquid immersion lithographyprocess, wherein the method comprises: forming a photoresist film on asubstrate; forming, on the resist film, a protective film having thefollowing properties of: being transparent with respect to exposurelight, having substantially no compatibility with a liquid for liquidimmersion lithography, and causing no mixing with the resist film;directly placing the liquid for liquid immersion lithography having apredetermined thickness at least on the protective film on the substratehaving the resist film and the protective film stacked thereon;irradiating the resist film with predetermined pattern light through theliquid for liquid immersion lithography and the protective film, andoptionally subjecting the resultant resist film to heat treatment;removing the protective film from the resist film irradiated; anddeveloping the resist film from which the protective film is removed toobtain a resist pattern.

Among the above-mentioned constructions, the liquid immersionlithography process preferably is of the construction in which theresist film is exposed with lithographic exposure light through a liquidfor liquid immersion lithography present at least on the resist film ina path of the exposure light toward the resist film, wherein the liquidhas a predetermined thickness and has a refractive index larger thanthat of air and smaller than that of the resist film, thus improving theresolution of a resist pattern.

EMBODIMENTS OF THE INVENTION

In the present invention having the above construction, the liquid forliquid immersion lithography that can be preferably used includes watersubstantially comprised of pure water or deionized water, or afluorocarbon inert liquid, more preferably water from the viewpoint ofcost reduction and ease of the post-treatment.

The resist films that can be used in the present invention include anyresist films obtained using a conventional resist composition, and arenot limited particularly. This is the most unique feature of the presentinvention.

The protective film according to the present invention has essentialproperties as described above, that the film is transparent to theexposure light and substantially incompatible with the refractive indexliquid and causes no mixing with the resist film, and the protectivefilm has excellent adhesion to the resist film and is easily removablefrom the resist film. A protective film material which can be used toform a protective film having such properties includes a compositionobtained by dissolving a fluororesin in a fluorocarbon solvent is used.

Examples of the fluororesin that can be used include linearperfluoroalkyl polyethers, cyclic perfluoroalkyl polyethers,polychlorotrifluoroethylenes, polytetrafluoroethylenes,tetrafluoroethylene-perfluoroalkoxyethylene copolymers, andtetrafluoroethylene-hexafluoropropylene copolymers.

In practice, among commercially available fluororesins, DEMNUM S-20,DEMNUM S-65, DEMNUM S-100, and DEMNUM S-200 which are linearperfluoroalkyl polyethers (each manufactured by DAIKIN INDUSTRIES,LTD.), CYTOP series which are cyclic perfluoroalkyl polyethers(manufactured by ASAHI GLASS CO., LTD.), and TEFLON (R)-AF1600 andTEFLON (R)-AF2400 (each manufactured by DuPont) can be used.

Among the fluororesins, mixed resins comprised of linear perfluoroalkylpolyethers and cyclic perfluoroalkyl polyethers are preferred.

The fluorocarbon solvent is not particularly limited as long as it candissolve the fluororesin. Examples of the fluorocarbon solvent that canbe used include perfluoroalkanes or perfluorocycloalkanes, such asperfluorohexane and perfluoroheptane, perfluoroalkenes having a doublebond remaining in the corresponding perfluoroalkanes orperfluorocycloalkanes, perfluoro cyclic ethers, such asperfluorotetrahydrofuran and perfluoro(2-butyltetrahydrofuran),perfluorotributylamine, perfluorotetrapentylamine, andperfluorotetrahexylamine.

Other organic solvents compatible with the fluorine solvent, surfactantsand so on can be appropriately used in admixture.

The concentration of the fluororesin is not particularly limited as longas a film can be formed therefrom. However, from the viewpoint ofachieving excellent coating properties, it is preferred that thefluororesin concentration be about 0.1 to about 30 wt %.

A preferred material for the protective film comprises a mixed resincomprised of a linear perfluoroalkyl polyether and a cyclicperfluoroalkyl polyether dissolved in perfluorotributylamine.

As mentioned above, the resist film materials that can be used in theliquid immersion lithography process of the present invention includecommonly used positive resists or negative photoresists. Specificexamples of positive or negative photoresists are shown below.

Resin components that can be used in the positive photoresist include anacrylic resin, a cycloolefin resin, or a silsesquioxane resin.

Preferred examples of the acrylic resin include a resin having, forexample, constitutional units (al) derived from a (meth)acrylic esterhaving an acid-dissociative, dissolution inhibiting group and comprising80 mol % or more, preferably 90 mol % (most preferably 100 mol %) ofconstitutional units derived from a (meth)acrylic ester includingconstitutional units derived from another (meth)acrylic ester other thanthe constitutional units (a1).

For achieving excellent resolution and excellent resistance to dryetching as well as fine pattern form, the resin component comprisesunits (a1) and a combination of a plurality of monomer units havingdifferent functions other than the units (a1), for example, thefollowing constitutional units.

Specifically, there can be mentioned constitutional units derived from a(meth)acrylic ester having a lactone unit (hereinafter, “(a2)” or “units(a2)”), constitutional units derived from a (meth)acrylic ester havingan alcoholic hydroxyl group-containing polycyclic group (hereinafter,“(a3)” or “units (a3)”), and constitutional units having a polycyclicgroup different from the acid-dissociative, dissolution inhibiting groupin the units (a1), the lactone unit in the units (a2), and the alcoholichydroxyl group-containing polycyclic group in the units (a3)(hereinafter, “(a4)” or “units (a4)”). (a2), (a3), and/or (a4) can beappropriately combined depending on, for example, the propertiesrequired. Preferably, when the resin component comprises (a1) and atleast one type of units selected from (a2), (a3), and (a4), excellentresolution and excellent resist pattern form can be achieved. Withrespect to each of the units (a1) to (a4), a plurality of differentunits may be used in combination.

The constitutional units derived from a methacrylic ester and theconstitutional units derived from an acrylic ester are advantageouslyused in such a manner that there are 10 to 85 mol %, preferably 20 to 80mol % of the constitutional units derived from the methacrylic ester and15 to 90 mol %, preferably 20 to 80 mol % of the constitutional unitsderived from the acrylic ester based on the total mole of theconstitutional units derived from the methacrylic ester and theconstitutional units derived from the acrylic ester.

Next, the units (a1) to (a4) are described in detail.

The units (a1) are constitutional units derived from a (meth)acrylicester having an acid-dissociative, dissolution inhibiting group. Theacid-dissociative, dissolution inhibiting group in (a1) is notparticularly limited as long as the group has alkali-dissolutioninhibiting properties such that it makes the entire resin componentalkali-insoluble before the exposure and the group dissociates due tothe action of acid generated after the exposure to change the entireresin component to be alkali-soluble. Generally, groups that form cyclicor chain tertiary alkyl esters with the carboxyl group of (meth)acrylicacid, tertiary alkoxycarbonyl groups, and chain alkoxyalkyl groups arewidely known.

Examples of the acid-dissociative, dissolution inhibiting group in (a1)that can be preferably used include acid-dissociative, dissolutioninhibiting groups containing aliphatic polycyclic groups.

Examples of the polycyclic groups include groups obtained by eliminatingone hydrogen element from a bicycloalkane, a tricycloalkane, or ateroracycloalkane, which may be unsubstituted or substituted with afluorine atom or a fluoroalkyl group. Specific examples thereof includegroups obtained by eliminating one hydrogen atom from a polycycloalkane,such as adamantane, norbornane, isobornane, tricyclodecane, ortetracyclododecane. Such a polycyclic group can be appropriatelyselected from a number of polycyclic groups proposed for ArF resists.Among these, preferred are an adamantyl group, a norbornyl group, and atetracyclododecanyl group from an industrial point of view.

Monomer units represented by the general formulae (1) to (7) below arepreferred as (a1) above. In the general formulae (1) to (7), Rrepresents a hydrogen atom or a methyl group, R₁ represents a loweralkyl group, each of R₂ and R₃ independently represents a lower alkylgroup, R₄ represents a tertiary alkyl group, R₅ represents a methylgroup, R₆ represents a lower alkyl group, and R₇ represents a loweralkyl group.

Each of R₁ to R₃, R₆, and R₇ is preferably a linear or branched loweralkyl group having 1 to 5 carbon atoms, and examples thereof include amethyl group, an ethyl group, a propyl group, an isopropyl group, ann-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, anisopentyl group, and a neopentyl group. From an industrial point ofview, preferred is a methyl group or an ethyl group.

R₄ is a tertiary alkyl group, such as a tert-butyl group or a tert-amylgroup, and preferred is a tert-butyl group from an industrial point ofview.

Among the above examples of units (a1), especially, constitutional unitsrepresented by the general formula (1), (2), or (3) are more preferredsince a pattern having high transparency and high resolution as well asexcellent resistence to dry etching can be formed therefrom.

The units (a2) above have a lactone unit, and hence are effective inenhancing the hydrophilicity with a developer solution.

The units (a2) may be any units that have a lactone unit and arecopolymerizable with the other constitutional units in the resincomponent.

Examples of monocyclic lactone units include groups obtained byeliminating one hydrogen atom from γ-butyro-lactone. Examples ofpolycyclic lactone units include groups obtained by eliminating onehydrogen atom from a lactone-containing polycycloalkane.

Monomer units represented by the general formulae (10) to (12) below arepreferred as (a2). In the general formulae, R represents a hydrogen atomor a methyl group.

A (meth) acrylic acid γ-butyrolactone ester having an ester linkage atthe α-carbon represented by the general formula (12) above and a(meth)acrylic acid norbornane lactone ester represented by the generalformula (10) or (11) above are especially preferred since they areeasily commercially available.

The units (a3) above are constitutional units derived from a(meth)acrylic ester having an alcoholic hydroxyl group-containingpolycyclic group.

The hydroxyl group in the alcoholic hydroxyl group-containing polycyclicgroup is a polar group, and therefore the use of this increases thecollective hydrophilicity of the resin component with a developersolution to improve the exposed portion in alkali-solubility. Thus, theresin component having (a3) preferably improves the resolution.

The polycyclic group in (a3) can be appropriately selected from thealiphatic polycyclic groups described above as examples in connectionwith (a1).

The alcoholic hydroxyl group-containing polycyclic group in (a3) is notparticularly limited. For example, a hydroxyl group-containing adamantylgroup is preferably used.

The hydroxyl group-containing adamantyl group represented by the generalformula (13) below is preferred since it has an effect of improving theresistance to dry etching and squareness of the pattern cross-sectionalform. In the general formula, 1 is an integer of 1 to 3.

The units (a3) may be any units that have the above-described alcoholichydroxyl group-containing polycyclic group and being copolymerizablewith the other constitutional units in the resin component.

Specifically, constitutional units represented by the general formula(14) below are preferred. In the general formula (14), R represents ahydrogen atom or a methyl group.

In the units (a4), the polycyclic group “different from theacid-dissociative, dissolution inhibiting group, the lactone unit, andthe alcoholic hydroxyl group-containing polycyclic group” means that thepolycyclic group in units (a4) in the resin component overlaps neitherthe acid-dissociative, dissolution inhibiting group in units (a1), thelactone unit in units (a2), nor the alcoholic hydroxyl group-containingpolycyclic group in units (a3), that is, units (a4) have neither theacid-dissociative, dissolution inhibiting group in units (a1), thelactone unit in units (a2), nor the alcoholic hydroxyl group-containingpolycyclic group in units (a3) that constitute the resin component.

The polycyclic group in the units (a4) is not particularly limited aslong as it is selected so as not to overlap the constitutional unitsused as the units (a1) to (a3) in the same resin component. For example,as the polycyclic group in units (a4), the aliphatic polycyclic group asexemplified in connection with the units (a1) can be used, and a numberof groups conventionally known in the ArF positive resist materials canbe used.

Especially preferred is at least one member selected from thetricyclodecanyl group, adamantyl group, and tetracyclododecanyl groupfrom the viewpoint of easy industrial availability.

The units (a4) may be any units that have the above-described polycyclicgroup and are copolymerizable with the other constitutional units in theresin component.

Preferred examples of (a4) are represented by the general formulae (15)to (17) below. In the general formulae, R represents a hydrogen atom ora methyl group.

With respect to the composition of the acrylic resin component, theamount of units (a1) may be 20 to 60 mol %, preferably 30 to 50 mol %,based on the total mole of the constitutional units constituting theresin component, since excellent resolution can be achieved.

The amount of units (a2) may be 20 to 60 mol %, preferably 30 to 50 mol%, based on the total mole of the constitutional units constituting theresin component, since excellent resolution can be achieved.

When the units (a3) are used, the amount of the units (a3) may be 5 to50 mol %, preferably 10 to 40 mol %, based on the total mole of theconstitutional units constituting the resin component, since excellentresist pattern form can be achieved.

When the units (a4) are used, the amount of the units (a4) may be 1 to30 mol %, preferably 5 to 20 mol %, based on the total mole of theconstitutional units constituting the resin component, since theseparate pattern or semi-dense pattern is excellent in resolution.

The units (a1) and at least one type of units selected from the units(a2), (a3), and (a4) can be appropriately used in combination dependingon the purpose. However, a ternary polymer comprising units (a1) andunits (a2) and (a3) is preferred since the resist pattern form, theexposure margin, the heat resistance, and the resolution are excellent.In this case, with respect to the respective contents of theconstitutional units (a1) to (a3), it is preferred that the content of(a1) is 20 to 60 mol %, the content of (a2) is 20 to 60 mol %, and thecontent of (a3) is 5 to 50 mol %.

A mass average molecular weight (as measured using polystyrene formolecular weight calibration; this applies to the following description)of the resin in the resin component in the present invention is notparticularly limited and it is preferably 5,000 to 30,000, morepreferably 8,000 to 20,000. When the mass average molecular weight islarger than the upper limit of the range, the solubility in a resistsolvent may become poor, and, when it is smaller than the lower limit ofthe range, the resistance to dry etching or the resist patterncross-sectional form may become poor.

The cycloolefin resin is preferably a resin comprising constitutionalunits (a5) represented by the general formula (18) below, which areoptionally copolymerized with one or more of the constitutional unitsobtained from (a1):

wherein R₈ represents a substituent mentioned above as an example of theacid-dissociative, dissolution inhibiting group in the units (a1), and mis an integer of 0 to 3.

In the units (a5), when m is 0, copolymers having units (a1) arepreferably used.

Examples of the silsesquioxane resins include resins havingconstitutional units (a6) represented by the following general formula(19), and resins having constitutional units (a7) represented by thefollowing general formula (20):

wherein R₉ represents an acid-dissociative, dissolution inhibiting groupcomprised of a hydrocarbon group containing an aliphatic monocyclic orpolycyclic group, Rlo represents a.linear, branched, or cyclic saturatedaliphatic hydrocarbon group, X represents an alkyl group having 1 to 8carbon atoms and having at least one hydrogen atom replaced by afluorine atom, and m is an integer of 1 to 3;

wherein R₁₁ represents a hydrogen atom or a linear, branched, or cyclicalkyl group, R₁₂ represents a linear, branched, or cyclic saturatedaliphatic hydrocarbon group, and X represents an alkyl group having 1 to8 carbon atoms and having at least one hydrogen atom replaced by afluorine atom.

In (a6) and (a7), the acid-dissociative, dissolution inhibiting group ofR₉ is a group which has alkali-dissolution inhibiting properties suchthat it makes the entire silsesquioxane resin alkali-insoluble beforethe exposure, and which dissociates due to the action of an acidgenerated from the acid generator after the exposure to change theentire silsesquioxane resin to be alkali-soluble.

Examples of such acid-dissociative, dissolution inhibiting groupsinclude acid-dissociative, dissolution inhibiting groups represented bythe general formulae (21) to (25) below include hydrocarbon groupscontaining a bulky aliphatic monocyclic or polycyclic group. By usingthe acid-dissociative, dissolution inhibiting group, the dissolutioninhibiting group after dissociation is unlikely to undergo gasification,thus preventing a degasification phenomenon.

R₉ has preferably 7 to 15, more preferably 9 to 13 carbon atoms sincethe dissolution inhibiting group after dissociation is unlikely toundergo gasification and appropriate solubility in a resist solvent orin a developer solution can be obtained.

The acid-dissociative, dissolution inhibiting group can be appropriatelyselected from a number of groups proposed for the resins for use in, forexample, ArF excimer laser resist compositions depending on the lightsource used as long as it is an acid-dissociative, dissolutioninhibiting group comprised of a hydrocarbon group containing analiphatic monocyclic or polycyclic group. Generally, those groups thatform cyclic tertiary alkyl esters with a carboxyl group of (meth)acrylicacid are widely known.

It is especially preferred that the acid-dissociative, dissolutioninhibiting group contains an aliphatic polycyclic group. The aliphaticpolycyclic group can be appropriately selected from a number ofaliphatic polycyclic groups proposed for the ArF resist. Examples of thealiphatic polycyclic groups include those groups obtained by eliminatingone hydrogen atom from a bicycloalkane, a tricycloalkane, or atetracycloalkane, and more specifically, those groups obtained byeliminating one hydrogen atom from a polycycloalkane such as adamantane,norbornane, isobornane, tricyclodecane, or tetracyclododecane.

Among the above general formulae, those silsesquioxane resins having anyone of the 2-methyl-2-adamantyl group represented by the general formula(23) and the 2-ethyl-2-adamantyl group represented by the generalformula (24) or both are preferred since they are unlikely to causedegasification and have excellent resist properties including resolutionand heat resistance.

Each of R₁₀ and R₁₁ has preferably 1 to 20, more preferably 5 to 12carbon atoms from the viewpoint of controlling the solubility in resistsolvents and the molecular size. Particularly, a saturated cyclicaliphatic hydrocarbon group preferably has advantages in that theresultant silsesquioxane resin has high transparency to high-energylight, and has a high glass transition temperature (Tg), which makeseasy controlling the acid generation from an acid generator during thePEB (post-exposure bake).

The saturated cyclic aliphatic hydrocarbon group may be either amonocyclic group or a polycyclic group. Examples of the polycyclicgroups include those groups obtained by eliminating two hydrogen atomsfrom a bicycloalkane, a tricycloalkane, or a teroracycloalkane, morespecifically, those groups obtained by eliminating two hydrogen atomsfrom a polycycloalkane such as adamantane, norbornane, isobornane,tricyclodecane, or tetracyclododecane.

More specific examples of R₁₀ and R₁₂ include those groups obtained byeliminating two hydrogen atoms from respective alicyclic compoundsrepresented by the general formulae (26) to (31) below or derivativesthereof.

The derivatives mean the alicyclic compounds of the chemical formulae(26) to (31) above having at least one hydrogen atom replaced by agroup, e.g., a lower alkyl group, such as a methyl group or an ethylgroup; an oxygen atom; or a halogen atom, such as fluorine, chlorine, orbromine. Among these, preferred is a group obtained by eliminating twohydrogen atoms from an alicyclic compound selected from the groupconsisting of the chemical formulae (26) to (31) since high transparencyis obtained and it is easily industrially available.

R₁₁ is a lower alkyl group having preferably 1 to 10, more preferably 1to 4 from the viewpoint of obtaining appropriate solubility in resistsolvents. More specific examples of alkyl groups include a methyl group,an ethyl group, a propyl group, an isopropyl group, an n-butyl group, asec-butyl group, a tert-butyl group, a cyclopentyl group, a cyclohexylgroup, a 2-ethylhexyl group, and an n-octyl group.

R₁₁ can be appropriately selected from the above candidate examplesdepending on the desired alkali-solubility of the silsesquioxane resin.When R₁₁ is a hydrogen atom, the alkali-solubility of the silsesquioxaneresin is highest. When the alkali-solubility is higher, there can beobtained an advantage in that the sensitivity is improved.

On the other hand, the larger the number of carbon atoms of the alkylgroup, or the more bulky the alkyl group, the lower thealkali-solubility of the silsesquioxane resin. When thealkali-solubility is lowered, the resistance to an alkaline developersolution is enhanced, and therefore the exposure margin in forming aresist pattern using the silsesquioxane resin is improved and thus thesize change caused during the exposure is reduced. In addition, unevendevelopment is prevented, suppressing roughness of the resultant resistpattern at the edge portion.

In the general formulae (19) and (20) above, X is especially preferablya linear alkyl group. The alkyl group may be a lower alkyl group having1 to 8, preferably 1 to 4 carbon atoms from the viewpoint of obtainingthe silsesquioxane resin having appropriate glass transition (Tg)temperature or solubility in a resist solvent. The alkyl grouppreferably has more hydrogen atoms replaced by fluorine atoms since thetransparency to high-energy light or electron beam of 200 nm or shorteris improved, and the alkyl group is most preferably a perfluoroalkylgroup having its all hydrogen atoms replaced by fluorine atoms. X's maybe the same or different. In the general formula (19), m may be aninteger of to 1 to 3, preferably 1 for permitting the acid-dissociative,dissolution inhibiting group to easily dissociate.

More specific examples of the silsesquioxane resins include those resinsrepresented by the following general formula (32) or (33):

wherein R₅, Root R₁₂, and n are as defined above.

The amount of the constitutional units represented by (a6) and (a7) maybe 30 to 100 mol %, preferably 70 to 100%, more preferably 100 mol %,based on the total mole of the constitutional units constituting thesilsesquioxane resin in the present invention.

The amount of the constitutional units represented by (a6) is preferably5 to 70 mol %, more preferably 10 to 40 mol %, based on the total moleof the constitutional units represented by (a6) and (a7). The amount ofthe constitutional units represented by (a7) is preferably 30 to 95 mol%, more preferably 60 to 90 mol %, based on the total mole of theconstitutional units represented by (a6) and (a7).

When the amount of the constitutional units represented by (a6) falls inthe above range, the amount of the acid-dissociative, dissolutioninhibiting group is naturally determined, so that the silsesquioxaneresin as a base resin of the positive resist composition advantageouslychanges in alkali-solubility before and after the exposure.

The silsesquioxane resin may have constitutional units other than theconstitutional units represented by (a6) and (a7) in such an amount thatthe effect aimed at by the present invention is not sacrificed. Examplesthereof include those units used in a silsesquioxane resin for ArFexcimer laser resist compositions, e.g., alkylsilsesquioxane unitsrepresented by the general formula (34) below, having an alkyl group(R′), such as a methyl group, an ethyl group, a propyl group, or a butylgroup.

The mass average molecular weight (Mw) (as measured by gel permeationchromatography using polystyrene for molecular weight calibration) ofthe silsesquioxane resin is not particularly limited, and it ispreferably 2,000 to 15,000, more preferably 3,000 to 8,000. When themass average molecular weight is larger than the upper limit of therange, the solubility in a resist solvent may become poor, and, when itis smaller than the lower limit of the range, the resist patterncross-sectional form may become poor.

The mass average molecular weight (Mw)/number average molecular weight(Mn), i.e., polymer distribution is not particularly limited, and it ispreferably 1.0 to 6.0, more preferably 1.5 to 2.5. When it is largerthan the upper limit of the range, the resolution and the pattern formmay become poor.

The silsesquioxane resin in the present invention is a polymer having inits basic skeleton a silsesquioxane comprising the constitutional unitsrepresented by (a6) and (a7), and hence has high transparency tohigh-energy light or electron beam of 200 nm or shorter. Therefore, thepositive resist composition containing the silsesquioxane resin in thepresent invention is advantageously used in lithography using a lightsource at a wavelength shorter than that of, e.g., an ArF excimer laser,and, particularly in a single-layer process, the resist composition canform a fine resist pattern having a line width as small as 150 nm orless, and further 120 nm or less. When using a two-layer resist laminateas an upper layer, the resist composition is advantageously used in aprocess forming a fine resist pattern as small as 120 nm or less, andfurther 100 nm or less.

The resin component used in the negative resist composition is notparticularly limited as long as it is a resin component commonly used.Specific preferred examples thereof are as follows.

As the resin component, there is preferably used a resin (a8)constituting a resin component that becomes alkali-insoluble due toacid, and having in its molecule two types of functional groups whichcan react with each other to form an ester, and which undergodehydration due to the action of the acid generated from an acidgenerator added to the resist material together with the resin to forman ester, thus making the resin component alkali-insoluble. The twotypes of functional groups which can react with each other to form anester mean, for example, a hydroxyl group and a carboxyl group or acarboxylic acid ester for forming a carboxylic acid ester. In otherwords, they mean two types of functional groups for forming an ester.Preferred examples of such resins include those resins having ahydroxyalkyl group and at least one of a carboxyl group and a carboxylicacid ester group at the side chain of the main skeleton of the resin.

Further, the resin component is preferably a resin component (a9)comprised of a polymer having dicarboxylic acid monoester units.

In other words, (a8) is a resin component having at least constitutionalunits represented by the following general formula (35):

wherein R₁₃ represents a hydrogen atom, a C₁-C₆ alkyl group, or an alkylgroup having a polycyclic ring skeleton, such as a bornyl group, anadamantyl group, a tetracyclododecyl group, or a tricyclodecyl group.

Preferred examples of such resins include polymers (homopolymers orcopolymers) (a8-1) comprised of at least one type of monomers selectedfrom an α-(hydroxyalkyl)-acrylic acid and an alkylα-(hydroxyalkyl)acrylate, and copolymers (a8-2) comprised of at leastone type of monomers selected from an ax-(hydroxyalkyl)acrylic acid andan alkyl α-(hydroxyalkyl)acrylate and at least one type of monomersselected from another ethylenically unsaturated carboxylic acid and anester of another ethylenically unsaturated carboxylic acid.

The polymers (a8-1) preferably include copolymers of anα-(hydroxyalkyl)acrylic acid and an alkyl α-(hydroxy-alkyl)acrylate,and, the copolymer (a8-2) preferably include copolymers that contain, asthe another ethylenically unsaturated carboxylic acid or ester ofanother ethylenically unsaturated carboxylic acid, at least one memberselected from acrylic acid, methacrylic acid, an alkyl acrylate, and analkyl methacrylate.

Examples of the hydroxyalkyl groups in the α-(hydroxyalkyl)acrylic acidor alkyl α-(hydroxyalkyl)-acrylate include lower hydroxyalkyl groups,such as a hydroxymethyl group, a hydroxyethyl group, a hydroxypropylgroup, and a hydroxybutyl group. Among these, preferred is ahydroxyethyl group or a hydroxymethyl group since it readily forms anester.

Examples of the alkyl groups in the alkyl ester portion of the alkylα-(hydroxyalkyl)acrylate include lower alkyl groups, such as a methylgroup, an ethyl group, a propyl group, an isopropyl group, an n-butylgroup, a sec-butyl group, a tert-butyl group, and an amyl group; andbridged polycyclic ring hydrocarbon groups, such as abicyclo[2.2.1]heptyl group, a bornyl group, an adamantyl group, atetracyclo[4.4.0.1^(2.5).1^(7.10)]dodecyl group, and atricyclo[5.2.1.0^(2.6)]decyl group. When the alkyl group in the esterportion is a polycyclic ring hydrocarbon group, the resultant polymer iseffective in enhancing the resistance to dry etching. Among these alkylgroups, especially preferred are lower alkyl groups, such as a methylgroup, an ethyl group, a propyl group, and a butyl group, since aninexpensive and easily available alcohol component for forming an estercan be used.

Like a carboxyl group, a lower alkyl ester undergoes esterification witha hydroxyalkyl group, but an ester of a bridged polycyclic ringhydrocarbon is unlikely to undergo such esterification. Therefore, whenthe ester of a bridged polycyclic ring hydrocarbon is introduced intothe resin, it is preferred that a carboxyl group be also present in theside chain of the resin.

On the other hand, examples of another ethylenically unsaturatedcarboxylic acids and esters of the ethylenically unsaturated carboxylicacid in (a8-2) include unsaturated carboxylic acids, such as acrylicacid, methacrylic acid, maleic acid, and fumaric acid, and alkyl estersof the unsaturated carboxylic acid, such as methyl, ethyl, propyl,isopropyl, n-butyl, isobutyl, n-hexyl, and octyl esters. As the alkylgroup in the ester portion, there can be used an ester of acrylic acidor methacrylic acid having a bridged polycyclic ring hydrocarbon group,such as a bicyclo[2.2.1]heptyl group, a bornyl group, an adamantylgroup, a tetracyclo[4.4.0.1^(2.5).1^(7.10)]dodecyl group, or atricyclo[5.2.1.0^(2.6)]decyl group. Among these, preferred are acrylicacid, methacrylic acid, and lower alkyl esters thereof, such as methyl,ethyl, propyl, and n-butyl esters, since they are inexpensive and easilyavailable.

In the resin in resin component (a8-2), the molar ratio of at least onetype of monomer units selected from an α-(hydroxyalkyl)acrylic acid andan alkyl α-(hydroxyalkyl)acrylate to at least one type of monomer unitsselected from anther ethylenically unsaturated carboxylic acid and anethylenically unsaturated carboxylic acid ester is preferably in therange of from 20:80 to 95:5, especially preferably 50:50 to 90:10. Whenthe ratio between the units falls in the above range, an ester is easilyformed in the molecule or between the molecules, so that excellentresist patterns can be obtained.

The resin component (a9) is a resin component having at leastconstitutional units represented by the following general formula (36)or (37):

wherein each of R₁₄ and R₁₅ represents an alkyl chain having 0 to 8carbon atoms, R₁₆ represents a substituent having at least two or morealicyclic structures, and each of R₁₇ and R₁₈ represents a hydrogen atomor an alkyl group having 1 to 8 carbon atoms.

The negative resist composition containing a resin component having thedicarboxylic acid monoester monomer units is preferred from theviewpoint of improved resolution and suppressed line edge roughness. Inaddition, the negative resist composition improves the swellingresistance and is more preferably used in the liquid immersionlithography process.

Examples of the dicarboxylic acid monoester compounds include fumaricacid, itaconic acid, mesaconic acid, glutaconic acid, and traumaticacid.

Preferred examples of resins having the dicarboxylic acid monoesterunits include polymers or copolymers (a9-1) comprised of dicarboxylicacid monoester monomers, and copolymers (a9-2) comprised of dicarboxylicacid monoester monomers and at least one type of monomers selected fromthe α-(hydroxyalkyl)acrylic acid, alkyl α-(hydroxyalkyl)-acrylate,another ethylenically unsaturated carboxylic acid, and ester of anotherethylenically unsaturated carboxylic acid.

The resin components used in the negative resist may be usedindividually or in combination. The resin component may have a weightaverage molecular weight of 1,000 to 50,000, preferably 2,000 to 3,0000.

The positive resist that includes the acrylic resin ((a1) to (a4)) amongthe above resins corresponds to a positive resist containing a resinhaving a relatively high resistance to water liquid immersion. However,the resolution of a pattern formed from this resist tends to be loweredas the size is closer to the resolution limit in the liquid immersionlithography. The cause of lowering of the resolution is not a singlefactor, and, for removing such factors, it is considerably effective toform the protective film of the present invention to completely separatethe immersion liquid from the resist film.

The positive resist that includes the silsesquioxane resin ((a6) and(a7)) or the negative resist that includes any one of the specificresins (aB) and (a9) or both is considered to have poor liquid immersionresistance, as compared to the positive resist using the acrylic resin,and the suitability of this resist for the liquid immersion lithographycan be improved by using the protective film of the present invention.

Further, as seen in the Comparative Examples in the present invention,it is known that the resist that includes a cycloolefin resin has a verypoor liquid immersion lithography resistance, which makes it impossibleto form a pattern. Even the positive resist containing such a resin canbe applied to the liquid immersion lithography by using the protectivefilm of the present invention.

The acid generator used in combination with the resin component of thepositive or negative resist may be any acid generators appropriatelyselected from known acid generators used in a conventional chemicallyamplified resist.

Specific examples of the acid generators include onium salts, such asdiphenyliodonium trifluoromethanesulfonate,(4-methoxyphenyl)phenyliodonium trifluotomethanesulfonate,bis(p-tert-butylphenyl)iodonium trifluoromethanesulfonate,triphenylsulfonium trifluoromethanesulfonate,(4-methoxy-phenyl)diphenylsulfonium trifluoromethanesulfonate,(4-methylphenyl)diphenylsulfonium trifluoromethanesulfonate,(4-methylphenyl)diphenylsulfonium nonafluorobutanesulfonate,(p-tert-butylphenyl)diphenylsulfonium trifluoromethane-sulfonate,diphenyliodonium nonafluorobutanesulfonate,bis(p-tert-butylphenyl)iodonium nonafluorobutanesulfonate,triphenylsulfonium nonafluorobutanesulfonate,(4-trifluoro-methylphenyl)diphenylsulfonium trifluoromethanesulfonate,(4-trifluoromethylphenyl)diphenylsulfonium nonafluoro-butanesulfonate,and tri(p-tert-butylphenyl)sulfonium trifluoromethanesulfonate.

Of the onium salts, triphenylsulfonium salts are preferably used sincethey are unlikely to decompose to generate organic gas. The amount ofthe triphenylsulfonium salt incorporated is preferably 50 to 100 mol %,more preferably 70 to 100 mol %, most preferably 100 mol %, based on thetotal mole of the acid generators.

Among the triphenylsulfonium salts, a triphenylsulfonium saltrepresented by the general formula (38) below having aperfluoroalkylsulfonic acid ion as anion is especially preferably usedsince high sensitivity can be achieved:

wherein each of R₁₉, R₂₀, and R₂₁ independently represents a hydrogenatom, a lower alkyl group having 1 to 8, preferably 1 to 4 carbon atoms,or a halogen atom, such as chlorine, fluorine, or bromine; and p is aninteger of 1 to 12, preferably 1 to 8, and more preferably 1 to 4.

The acid generators may be used individually or in combination.

The amount of the acid generator incorporated may be 0.5 part by mass,preferably 1 to 10 parts by mass, based on 100 parts by mass of theresin component. When the amount of the acid generator is less than 0.5part by mass, pattern formation is not satisfactorily achieved, and,when the amount is more than 30 parts by mass, a uniform solution isdifficult to obtain, leading to the lowering of the storage stability.

The positive or negative resist composition in the present invention isproduced by dissolving the resin component and the acid generator andthe arbitrary component mentioned below preferably in an organicsolvent.

The organic solvent may be any organic solvents as long as they candissolve the resin component and the acid generator to form a uniformsolution. Any one or more types of solvent appropriately selected fromthe known solvents for conventional chemically amplified resists can beused.

Examples of the organic solvents include ketones, such as acetone,methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, and2-heptanone; polyhydric alcohols and derivatives thereof, such asmonomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether, ormonophenyl ether of ethylene glycol, ethylene glycol monoacetate,diethylene glycol, diethylene glycol monoacetate, propylene glycol,propylene glycol monoacetate, dipropylene glycol, or dipropylene glycolmonoacetate; cyclic ethers, such as dioxane; and esters, such as methyllactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate,methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, and ethylethoxypropionate. These organic solvents may be used individually or inthe form of a mixed solvent composed of two or more of them.

To improve the form and stability with time of the resist pattern, thepositive or negative resist may further contain, as a quencher, a knownamine, preferably a secondary lower aliphatic amine or a tertiary loweraliphatic amine, or an organic acid, such as an organic carboxylic acidor an oxo-acid of phosphorus.

The lower aliphatic amine means an alkylamine or alkylalcoholaminehaving 5 carbon atoms or less, and examples of the secondary or tertiaryamines include trimethylamine, diethylamine, triethylamine,di-n-propylamine, tri-n-propylamine, tribentylamine, diethanolamine, andtriethanolamine, and especially preferred is an alkanolamine, such astriethanolamine. These amines may be used individually or incombination.

The amine is used in an amount in the range of generally from 0.01 to2.0% by mass, based on the mass of the resin component.

Example of preferred organic carboxylic acids include malonic acid,citric acid, malic acid, succinic acid, benzoic acid, and salicylicacid.

Examples of the oxo-acids of phosphorus and derivatives thereof includephosphoric acid and derivatives thereof, e.g., esters, such asphosphoric acid, di-n-butyl phosphate, and diphenyl phosphate;phosphonic acid and derivatives thereof, e.g., esters, such asphosphonic acid, dimethyl phosphonate, di-n-butyl phosphonate,phenylphosphonic acid, diphenyl phosphonate, and dibenzyl phosphonate;and phosphinic acid, such as phosphinic acid and phenylphosphinic acid,and derivatives thereof, e.g., esters. Of these, especially preferred isphosphonic acid.

The organic acid is used in an amount of 0.01 to 5.0 parts by mass,based on 100 parts by mass of the resin component. The organic acids maybe used individually or in combination.

The amount of the organic acid used is preferably in the range of theequimolar amount to the amine or smaller.

The positive resist composition of the present invention may if desiredcontain an additive miscible with the composition, for example, anadditional resin for improving the performance of the resist film, or asurfactant, a dissolution inhibitor, a plasticizer, a stabilizer, acoloring agent, or a halation preventing agent for improving the coatingproperties.

The negative resist composition of the present invention may ifnecessary be blended with a cross-linking agent for further increasingthe cross-linking density to improve the form or resolution of theresist pattern or the resistance to dry etching.

The cross-linking agent is not particularly limited, and anycross-linking agent appropriately selected from known cross-linkingagents for use in a conventional chemically amplified negative resistcan be used. Examples of the cross-linking agents include alicyclichydrocarbons having any one of a hydroxyl group and a hydroxyalkyl groupor both and oxygen-containing derivatives thereof, such as2,3-dihydroxy-5-hydroxymethylnorbornane,2-hydroxy-5,6-bis(hydroxymethyl)norbornane, cyclohexanedimethanol,3,4,8(or 9)-trihydroxytricyclodecane, 2-methyl-2-adamantanol,1,4-dioxan-2,3-diol, and 1,3,5-trihydroxycyclohexane; and compoundsobtained by reacting an amino group-containing compound, such asmelamine, acetoguanamine, benzoguanamine, urea, ethyleneurea, orglycoluril, with formaldehyde or formaldehyde and a lower alcohol toreplace a hydrogen atom in the amino group by a hydroxymethyl group or alower alkoxymethyl group. Specific examples thereof includehexamethoxymethylmelamine, bismethoxymethylurea,bismethoxymethylbismethoxyethyleneurea, tetramethoxymethylglycoluril,and tetrabutoxymethylglycoluril, with tetrabutoxymethylglycoluril beingespecially preferred.

The cross-linking agents may be used individually or in combination.

Next, a method for forming a resist pattern by a liquid immersionlithography process using the protective film of the present inventionis described.

A conventional resist composition is first applied onto a substrate,such as a silicon wafer, by means of, e.g., a spinner, and thensubjected to prebake (PAB treatment).

An organic or inorganic antireflection coating film can be formedbetween the substrate and the coating layer of the resist composition toform a two-layer laminate.

The above steps can be conducted using a conventionally known method. Itis preferred that the conditions for procedure are appropriatelyselected depending on the formulation or properties of the resistcomposition used.

Subsequently, a protective film-forming material composition, forexample, “composition obtained by dissolving a mixed resin comprised ofchain perfluoroalkyl polyether and cyclic perfluoroalkyl polyether inperfluorotributylamine” is uniformly applied to the surface of theabove-cured resist film (comprised of a single layer or multiplelayers), and then cured to form a resist protecting film.

The thus obtained substrate having the resist film covered with theprotective film is immersed in a refractive index liquid (liquid havinga refractive index larger than the refractive index of air and smallerthan the refractive index of the resist film).

The resist film on the substrate immersed in the liquid is selectivelyexposed through a desired mask pattern. In this instance, the exposurelight passes through the refractive index liquid and protective film andreaches the resist film.

In this case, the resist film is completely protected by the protectivefilm from the refractive index liquid, so that the resist film does notundergo a change in properties, such as swelling, due to attack of therefractive index liquid, or a component of the resist film is notdissolved in the refractive index liquid to change the refractive indexliquid in optical properties, e.g., refractive index.

The wavelength of light used in the above exposure is not particularlylimited, and radiation, such as an ArF excimer laser, a KrF excimerlaser, an F₂ excimer laser, an EUV (extreme ultraviolet light), a VUV(vacuum ultraviolet light), an electron beam, an X-ray, or a soft X-raycan be used. The wavelength is determined mainly by the characteristicof the resist film.

As mentioned above, in the method for forming a resist pattern of thepresent invention, the resist film is exposed through a liquid having arefractive index larger than that of air and smaller than that of theresist film used (refractive index liquid), the liquid being present onthe resist film. Examples of such refractive index liquid include waterand fluorocarbon inert liquids. Specific examples of the fluorocarboninert liquids include liquids comprised mainly of fluorocarboncompounds, such as C₃HCl₂F₅, C₄F₉OCH₃, C₄F₉OC₂H₅, or C₅H₃F₇. Amongthese, water is preferably used from the viewpoint of the cost, safety,environmental issues, and general purpose properties.

The refractive index of the refractive index liquid used is notparticularly limited as long as the refractive index is “larger than therefractive index of air and smaller than the refractive index of theresist composition used”.

After completion of the step of the exposure in an immersed state, thesubstrate is taken out of the refractive index liquid, and the liquid isremoved from the substrate, and then the protective film is removed. Inthe removal of the protective film, a fluorine solvent capable ofdissolving the fluororesin can be directly used. From the viewpoint offacilitating the drying after washing, a solvent having a boiling pointof about 150° C. or lower is preferably used, and preferred isperfluoro(2-butyltetra-hydrofuran)(boiling point: 102° C.) from thispoint of view.

Subsequently, the resist film exposed is subjected to PEB (post-exposurebake), and then developed using an alkaline developer solution comprisedof an alkaline aqueous solution. The PEB may be conducted before thestep of removing the protective film. Post-bake may be conducted afterthe development treatment. Preferably, rinsing is carried out using purewater. The rinsing with water is made by, for example, allowing water tofall dropwise or spraying water against the surface of the substratewhile rotating the substrate to wash away the developer solution on thesubstrate and the resist composition dissolved by the developersolution. Then, drying is conducted to obtain a resist pattern having aform patterned in the resist film according to the mask pattern.

By forming a resist pattern by the above method, a resist pattern havinga fine line width, especially a line and space pattern having a smallpitch with excellent resolution can be produced. The pitch in the lineand space pattern means the total distance of a resist pattern width anda space width in the direction of the line width of the pattern.

EXAMPLES

While Examples of the present invention will be explained below, theseexamples merely exemplify the invention preferably, and do not limit theinvention. In the following explanations, Comparative Examples aredescribed along with the Examples.

Example 1

The resin component, acid generator, and nitrogen-containing organiccompound shown below were uniformly dissolved in an organic solvent toprepare positive resist composition 1.

As the resin component, 100 parts by mass of a methacrylate-acrylatecopolymer comprising three types of constitutional units represented bythe chemical formulae (39a), (39b), and (39c) below was used. In theconstitutional units used in the preparation of the resin component, p,q, and r are as follows: p=50 mol %, q=30 mol %, and r=20 mol %. Theresin component prepared had a mass average molecular weight of 10,000.

As the acid generator, 3.5 parts by mass of triphenylsulfoniumnonafluorobutanesulfonate and 1.0 part by mass of(4-methylphenyl)diphenylsulfonium trifluoromethanesulfonate were used.

As the organic solvent, 1,900 parts by mass of a mixed solvent ofpropylene glycol monomethyl ether acetate and ethyl lactate (mass ratio:6:4) was used.

Further, as the nitrogen-containing organic compound, 0.3 part by massof triethanolamine was used.

Using the above-prepared positive resist composition 1, a resist patternwas formed.

An organic antireflection coating composition “AR-19” (trade name;manufactured by Shipley Limited) was first applied onto a silicon waferusing a spinner, and dried by calcination on a hot plate at 215° C. for60 seconds to form an organic antireflection coating film having athickness of 82 nm. Then, positive resist composition 1 was applied ontothe antireflection coating film using a spinner, and dried by prebake ona hot plate at 115° C. for 90 seconds to form a resist film having athickness of 150 nm on the antireflection coating film.

A protective film material, which was obtained by dissolving a mixedresin comprised of DEMNUM S-20 (manufactured by DAIKIN INDUSTRIES, Ltd.)and CYTOP (manufactured by ASAHI GLASS CO., LTD.)(weight ratio=1:5) inperfluorotributylamine to have a resin concentration of 2.5 wt %, wasapplied onto the resist film by spin coating, and heated at 90° C. for60 seconds to form a protective film having a thickness of 37 nm.

Subsequently, the resist film was irradiated (exposed) through a maskpattern with pattern light using an ArF excimer laser (wavelength: 193nm) by means of an exposure system NSR-S302B (manufactured by NikonCorporation, NA (numerical aperture)=0.60, σ=0.75). Then, in a liquidimmersion lithography, while rotating the silicon wafer having theresist film exposed, pure water at 23° C. was allowed to fall dropwiseagainst the resist film for 5 minutes. This step corresponds to the stepin the practical production process in which the resist film completelyimmersed in the liquid is exposed. However, the step has a simplifiedconstruction such that pure water as a refractive index liquid(immersion liquid) is applied to the resist film after the exposure inorder to achieve an evaluation of only the effect of the immersionliquid on the resist film which is previously exposed. This is becausebased on the above-stated analysis on the liquid immersion lithographymethod, completion of the exposure in the optics is theoreticallyguaranteed.

After the step of allowing pure water to fall dropwise, the resultantresist film was subjected to PEB treatment under conditions at 115° C.for 90 seconds, and then the protective film was removed usingperfluoro(2-butyltetra-hydrofuran). Then, the resist film was developedusing an alkaline developer solution at 23° C. for 60 seconds. As thealkaline developer solution, a 2.38% by mass aqueous solution oftetramethylammonium hydroxide was used.

The thus obtained resist pattern having a 130 nm line and space of 1:1was examined under a scanning electron microscope (SEM). As a result,the pattern profile was found to be excellent such that no fluctuationwas observed.

Example 2

An antireflection coating film, an ArF positive resist, and a protectivefilm were formed on a substrate in accordance with the same procedure asthat in Example 1.

Using laboratory equipment prepared by Nikon Corporation using a prismand a liquid and two-beam interferometry exposure at a wavelength of 193nm, the substrate having the protective film formed thereon wassubjected to immersion lithography (the bottom surface of the prism wasin contact with the protective film through water).

The resultant substrate was subjected to PEB treatment in the samemanner as that in Example 1, and the protective film was removed usingperfluoro(2-butyltetrahydrofuran). Then, the resist film was developedunder the same conditions as those used in Example 1.

The thus obtained resist pattern having a 65 nm line and space of 1:1was examined under a scanning electron microscope (SEM). As a result,the pattern profile was found to be excellent such that no fluctuationwas observed. Further, the pattern obtained was examined for across-sectional form under a focused ion beam SEM (Altura 835;manufactured by FEI). As a result, it was found that the cross-sectionalform had excellent squareness.

Comparative Example 1

A resist pattern was formed in accordance with substantially the sameprocedure as that in Example 2 except that no protective film wasformed.

As a result, although no change in the sensitivity was found, slightfluctuation (partial narrowing of lines) was observed in the patternprofile. Further, the pattern obtained was examined for across-sectional form under a focused ion beam SEM (Altura 835;manufactured by FEI). As a result, a slight T-top form was observed.

Comparative Example 2

The resin component, acid generator, and nitrogen-containing organiccompound shown below were uniformly dissolved in an organic solvent toprepare positive resist composition 2.

As the resin component, 100 parts by mass of a polymer comprisingconstitutional units represented by the chemical formula (40) below wasused. The resin component prepared had a mass average molecular weightof 10,000.

As the acid generator, 3.5 parts by mass of triphenylsulfoniumnonafluorobutanesulfonate and 1.0 part by mass of(4-methylphenyl)diphenylsulfonium trifluoromethanesulfonate were used.

As the organic solvent, 1,900 parts by mass of a mixed solvent ofpropylene glycol monomethyl ether acetate and ethyl lactate (mass ratio:6:4) was used.

Further, as the nitrogen-containing organic compound, 0.3 part by massof triethanolamine was used.

Using the above-prepared positive resist composition 2, a resist patternwas formed.

An organic antireflection coating composition “AR-19” (trade name;manufactured by Shipley Limited) was first applied onto a silicon waferusing a spinner, and dried by calcination on a hot plate at 215° C. for60 seconds to form an organic antireflection coating film having athickness of 82 nm. Then, positive resist composition 1 was applied ontothe antireflection coating film using a spinner, and dried by prebake ona hot plate at 115° C. for 90 seconds to form a resist film having athickness of 150 nm on the antireflection coating film.

Subsequently, the resist film was irradiated (exposed) through a maskpattern with pattern light using an ArF excimer laser (wavelength: 193nm) by means of an exposure system NSR-S302B (manufactured by NikonCorporation, NA (numerical aperture)=0.60, σ=0.75). Then, in a liquidimmersion lithography, while rotating the silicon wafer having theresist film exposed, pure water at 23° C. was allowed to fall dropwiseagainst the resist film for 5 minutes. This step corresponds to the stepin the practical production process in which the resist film completelyimmersed in the liquid is exposed. However, the step has a simplifiedconstruction such that pure water as a refractive index liquid(immersion liquid) is applied to the resist film after the exposure inorder to achieve an evaluation of only the effect of the immersionliquid on the resist film which is previously exposed. This is becausebased on the above-stated analysis on the liquid immersion lithographymethod, completion of the exposure in the optics is theoreticallyguaranteed.

Subsequently, the resultant resist film was subjected to PEB treatmentunder conditions at 115° C. for 90 seconds, and developed using analkaline developer solution at 23° C. for 60 seconds. As the alkalinedeveloper solution, a 2.38% by mass aqueous solution oftetramethylammonium hydroxide was used.

The thus obtained resist pattern having a 130 nm line and space of 1:1was examined under a scanning electron microscope (SEM), and asensitivity (Eth) was determined. As a result, it was found that thesensitivity measured was 9.1 mJ/cm² and the lowering of the sensitivitywas considerable as seen from the comparisons made below.

Separately, using resist composition 2 in the present ComparativeExample 2, a resist pattern was formed by exposure through a layer ofair by the method conventionally used without employing the liquidimmersion lithography treatment. As a result, the sensitivity was foundto be 8.4 mJ/cm². A ratio of the sensitivity in the liquid immersionlithography treatment to the sensitivity in the normal exposure(9.1/8.4) was determined to be 108.3.

Comparative Example 3

The resin component, acid generator, and nitrogen-containing organiccompound shown below were uniformly dissolved in an organic solvent toprepare positive resist composition 3.

As the resin component, 100 parts by mass of a copolymer comprisingconstitutional units comprising 63 mol % of hydroxystyrene units, 24 mol% of styrene units, and 13 mol % of tert-butyl acrylate units was used.The resin component prepared had a mass average molecular weight of12,000.

As the acid generator, 2.8 parts by mass of bis(tert-butylphenyliodoniumtrifluoromethanesulfonate and 1.0 part by mass ofdimethylmonophenylsulfonium trifluoromethanesulfonate were used.

As the organic solvent, 600 parts by mass of ethyl lactate was used.

As the nitrogen-containing organic compound, 0.26 part by mass oftriethanolamine was used, and 0.28 part by mass of phenylphosphonic acidwas used as another component.

Using the above-prepared positive resist composition 3, a resist patternwas formed.

An organic antireflection coating composition “AR-3” (trade name;manufactured by Shipley Limited) was first applied onto a silicon waferusing a spinner, and dried by calcination on a hot plate at 220° C. for60 seconds to form an organic antireflection coating film having athickness of 62 nm. Then, positive resist composition 3 was applied ontothe antireflection coating film using a spinner, and dried by prebake ona hot plate at 110° C. for 90 seconds to form a resist film having athickness of 280 nm on the antireflection coating film.

Subsequently, the resist film was irradiated (exposed) through a maskpattern with pattern light using a KrF excimer laser (wavelength: 248nm) by means of an exposure system NSR-S203 (manufactured by NikonCorporation, NA (numerical aperture)=0.60, σ=0.75). Then, in a liquidimmersion lithography, while rotating the silicon-wafer having theresist film exposed, pure water at 23° C. was allowed to fall dropwiseagainst the resist film for 5 minutes. This step corresponds to the stepin the practical production process in which the resist film completelyimmersed in the liquid is exposed. However, the step has a simplifiedconstruction such that pure water as a refractive index liquid(immersion liquid) is applied to the resist film after the exposure inorder to achieve an evaluation of only the effect of the immersionliquid on the resist film which is previously exposed. This is becausebased on the above-stated analysis on the liquid immersion lithographymethod, completion of the exposure in the optics is theoreticallyguaranteed.

Subsequently, the resultant resist film was subjected to PEB treatmentunder conditions at 115° C. for 90 seconds, and developed using analkaline developer solution at 23° C. for 60 seconds. As the alkalinedeveloper solution, a 2.38% by mass aqueous solution oftetramethylammonium hydroxide was used.

Thus obtained resist pattern having a 140 nm line and space of 1:1 wasexamined under a scanning electron microscope (SEM), and sensitivity(Eth) at that time was determined. As a result, it was found that thesensitivity was 22.0 mJ/cm². The resist pattern had a T-top form andsurface roughening was observed.

Separately, using resist composition 3 in the present ComparativeExample, a resist pattern was formed by exposure through a layer of airby the method conventionally used without employing the liquid immersionlithography treatment, and the sensitivity was found to be 20.0 mJ/cm².A ratio of the sensitivity in the liquid immersion lithography treatmentto the sensitivity in the normal exposure (22.0/20.0) was determined tobe 108.8. The resist pattern was excellent such that no surfaceroughening was observed.

Comparative Example 4

The resin component, acid generator, and nitrogen-containing organiccompound shown below were uniformly dissolved in an organic solvent toprepare positive resist composition 4.

As the resin component, a mixed resin of 70 parts by mass of a copolymercomprising constitutional units comprising 64 mol % of hydroxystyreneunits and 36 mol % of 1-ethoxy-1-ethyloxystyrene units and 30 parts bymass of a copolymer comprising constitutional units comprising 67 mol %of hydroxystyrene units and 33 mol % of tetrahydropyranyloxystyreneunits was used. The resin components prepared independently had a massaverage molecular weight of 8,000.

As the acid generator, 4 parts by mass ofbis(cyclohexylsulfonyl)diazomethane and 1 part by mass oftert-butylphenyliodonium trifluoromethanesulfonate were used.

As the organic solvent, 600 parts by mass of a mixed solvent ofpropylene glycol monomethyl ether acetate and ethyl lactate (mass ratio:6:4) was used.

As the nitrogen-containing organic compound, 0.52 part by mass oftriisopropanolamine was used, and 0.54 part by mass of dodecanoic acidwas used as another component.

Using the above-prepared positive resist composition 4, a resist patternwas formed.

An organic antireflection coating composition “DUV-44” (trade name;manufactured by Brewer Science) was first applied onto a silicon waferusing a spinner, and dried by calcination on a hot plate at 225° C. for90 seconds to form an organic antireflection coating film having athickness of 65 nm. Then, positive resist composition 4 was applied ontothe antireflection coating film using a spinner, and dried by prebake ona hot plate at 90° C. for 90 seconds to form a resist film having athickness of 280 nm on the antireflection coating film.

Subsequently, the resist film was irradiated (exposed) through a maskpattern with pattern light using a KrF excimer laser (wavelength: 248nm) by means of an exposure system NSR-S203 (manufactured by NikonCorporation, NA (numerical aperture)=060, (=0.75). Then, in a liquidimmersion lithography, while rotating the silicon wafer having theresist film exposed, pure water at 23° C. was allowed to fall dropwiseagainst the resist film for 5 minutes. This step corresponds to the stepin the practical production process in which the resist film completelyimmersed in the liquid is exposed. However, the step has a simplifiedconstruction such that pure water as a refractive index liquid(immersion liquid) is applied to the resist film after the exposure inorder to achieve an evaluation of only the effect of the immersionliquid on the resist film which is previously exposed. This is becausebased on the above-stated analysis on the liquid immersion lithographymethod, completion of the exposure in the optics is theoreticallyguaranteed.

Next, the resultant resist film was subjected to PEB treatment underconditions at 110° C. for 90 seconds, and developed using an alkalinedeveloper solution at 23° C. for 60 seconds. As the alkaline developersolution, a 2.38% by mass aqueous solution of tetramethylammoniumhydroxide was used.

The thus obtained resist pattern having a 140 nm line and space of 1:1was examined under a scanning electron microscope (SEM), and sensitivity(Eth) at that time was determined. As a result, it was found that thesensitivity was 26.5 mJ/cm². The resist pattern had a.T-top form andsurface roughening was observed.

Separately, using resist composition 4 in the present ComparativeExample, a resist pattern-was formed by exposure through a layer of airby the method conventionally used without employing the liquid immersionlithography treatment, and the sensitivity was found to be 16.5 mJ/cm².A ratio of the sensitivity in the liquid immersion lithography treatmentto the sensitivity in the normal exposure (26.5/16.5) was determined tobe 156.6. The resist pattern was excellent such that no surfaceroughening was observed.

Examples 1 and 2 indicate that, in the liquid immersion lithography inwhich a protective film is formed, a pattern of 130 nm line and spacehaving excellent profile can be obtained without lowering the propertiesrequired for pattern formation, e.g., sensitivity. In addition, it isapparent that the resist film used in the Examples, which is a positiveresist film, can be applied to a negative resist film.

Example 3

The resin component, acid generator, and nitrogen-containing organiccompound shown below were uniformly dissolved in an organic solvent toprepare a positive resist.

As the resin component, 100 parts by mass of a polymer comprisingconstitutional units indicated by the above formula (40). The resincomponent prepared had a mass average molecular weight of 10,000.

As the acid generator, 3.5 parts by mass of triphenylsulfoniumnonafluorobutanesulfonate and 1.0 part by mass of(4-methylphenyl)diphenylsulfonium trifluoromethanesulfonate were used.

As the organic solvent, 1,900 parts by mass of a mixed solvent ofpropylene glycol monomethyl ether acetate and ethyl lactate (mass ratio:6:4) was used.

As the nitrogen-containing organic compound, 0.3 part by mass oftriethanolamine was used.

An antireflection coating film, an ArF positive resist, and a protectivefilm were formed on a substrate in accordance with substantially thesame procedure as in Example 1 except that the above-prepared positiveresist composition was used (the thickness of the resist film waschanged to 140 nm).

The substrate having the protective film formed thereon was subjected toimmersion lithography in the same manner as in Example 2.

The protective film was removed from the resist film under the sameconditions as those used in Example 1, and the resist film was subjectedto PEB treatment, followed by development.

The thus obtained resist pattern having a 90 nm line and space of 1:1was examined under a scanning electron microscope (SEM), and, as aresult, the pattern profile was found to be excellent such that nofluctuation (pattern narrowing) was observed.

Comparative Example 5

A resist pattern having a 90 nm line and space of 1:1 was formed inaccordance with entirely the same procedure as in Example 3 except thatthe positive photoresist shown in Example 3 was used and that noprotective film was formed, and it was examined under a scanningelectron microscope (SEM), but the fluctuation and swelling of thepattern were too large to observe the pattern.

Example 4

The resin component, acid generator, and nitrogen-containing organiccompound shown below were uniformly dissolved in an organic solvent toprepare a positive resist composition.

As the resin component, a polymer comprising constitutional unitsrepresented by the general formulae (41) and (42) below (85 parts bymass of the units of formula (41) and 15 parts by mass of the units offormula (42)) was used. The resin component had a mass average molecularweight of 10,000.

As the acid generator, 3.0 parts by mass of triphenylsulfoniumnonafluorobutanesulfonate was used.

As the organic solvent, 1,900 parts by mass of a mixed solvent ofpropylene glycol monomethyl ether acetate and ethyl lactate (mass ratio:6:4) was used.

As the nitrogen-containing organic compound, 0.25 part by mass oftriethanolamine was used.

wherein, in formula (42), j=50 mol %, k=30 mol %, and 1=20 mol %.

An antireflection coating film, an ArF positive resist, and a protectivefilm were formed on a substrate in accordance with the same procedure asin Example 1 except that the above-prepared positive resist compositionwas used (the thickness of the resist film was changed to 140 nm).

The substrate having the protective film formed thereon was subjected toimmersion lithography in the same manner as in Example 2.

The protective film was removed from the resist film under the sameconditions as those used in Example 1, and the resist film was subjectedto PEB treatment, followed by development.

The thus obtained resist pattern having a 90 nm line and space of 1:1was examined under a scanning electron microscope (SEM), and, as aresult, the pattern profile was found to be excellent such that nofluctuation (pattern narrowing) was observed.

Comparative Example 6

A resist pattern having a 90 nm line and space of 1:1 was formed inaccordance with entirely the same procedure as in Example 4 except thatthe positive photoresist shown in Example 3 was used and that noprotective film was formed, and it was examined under a scanningelectron microscope (SEM), but the fluctuation and swelling of thepattern occurred slightly.

Example 5

The resin component, acid generator, and nitrogen-containing organiccompound shown below were uniformly dissolved in an organic solvent toprepare a negative resist composition.

As the resin component, a polymer comprising constitutional unitsrepresented by the general formula (43) was used.

Based on the mass of the resin component, 10% by mass of a cross-linkingagent comprised of tetrabutoxymethylated glycoluril, 1% by mass of anacid generator comprised of triphenylsulfoniumnonafluorobutanesulfonate, and 0.6% by mass of an amine componentcomprised of 4-phenylpyridine were dissolved in propylene glycolmonomethyl ether, and the resultant negative resist material having asolids content of 8.1% by mass was used.

wherein m:n is 84:16 (mol %).

Using the above-prepared negative resist composition, a resist patternwas formed.

An organic antireflection coating composition “AR-19” (trade name;manufactured by Shipley Limited) was first applied onto a silicon waferusing a spinner, and dried by calcination on a hot plate at 215° C. for60 seconds to form an organic antireflection coating film having athickness of 32 nm. Then, the negative resist composition was appliedonto the antireflection coating film using a spinner, and dried byprebake on a hot plate at 110° C. for 60 seconds to form a resist filmhaving a thickness of 300 nm on the antireflection coating film.

A protective film material, which was obtained by dissolving a mixedresin comprised of DEMNUM S-10 (manufactured by DAIKIN INDUSTRIES, Ltd.)and CYTOP (manufactured by ASAHI GLASS CO., LTD.)(weight ratio=1:5) inperfluorotributylamine to have the resin concentration 2.5 wt %, wasapplied onto the resist film by spin coating, and heated at 90° C. for60 seconds to form a protective film having a thickness of 37 nm.

The substrate having the protective film formed thereon was subjected toexposure in the same manner as in Example 1, and then water was allowedto fall dropwise against the resist film (the treatment of allowingwater to fall dropwise was continued for 2 minutes).

The protective film was removed from the resist film under the sameconditions as those used in Example 1, and the resist film was subjectedto PEB treatment, followed by development.

The thus obtained resist pattern having a 160 nm line and space of 1:1was examined under a scanning electron microscope (SEM), and, as aresult, the pattern profile was found to be excellent such that nofluctuation (pattern narrowing) and swelling were observed at all.

Comparative Example 7

A resist pattern having a 160 nm line and space of 1:1 was formed inaccordance with entirely the same procedure as in Example 4 except thatthe negative photoresist shown in Example 5 was used and that noprotective film was formed, and it was examined under a scanningelectron microscope (SEM), but the fluctuation and swelling of thepattern occurred slightly.

In the descriptions in the present invention, the following wording anddifferent terms: “liquid having a refractive index larger than that ofair and smaller than that of the resist film”; liquid refractive indexmedium; refractive index liquid; and immersion liquid, which were usedfor convenience of explanation, designate the same medium.

Example 6

The resin component, acid generator, and nitrogen-containing organiccompound shown below were uniformly dissolved in an organic solvent toprepare a positive resist composition.

As the resin component, 100 parts by mass of a methacrylate copolymercomprising three types of constitutional units represented by thegeneral formula (44) below was used. In the constitutional units used inthe preparation of the resin component, s, t, and u are as follows: s=40mol %, t=40 mol %, and u=20 mol %. The resin component prepared had amass average molecular weight of 10,000.

As the acid generator, 0.8 part by mass oftri-(4-tert-butylphenyl)sulfonium trifluoromethanesulfonate and 2.0parts by mass of (4-methylphenyl)diphenylsulfoniumnonafluorobutanesulfonate were used.

As the organic solvent, a mixed solvent of 1,520 parts by mass of amixed solvent of propylene glycol monomethyl ether acetate and ethyllactate (mass ratio: 6:4) and 380 parts by mass of γ-butyrolactone wasused.

As the nitrogen-containing organic compound, 0.25 part by mass oftriethanolamine was used.

Using the above-prepared positive resist composition, a resist patternwas formed.

An organic antireflection coating composition “AR-19” (trade name;manufactured by Shipley Limited) was first applied onto a silicon waferusing a spinner, and dried by calcination on a hot plate at 215° C. for60 seconds to form an organic antireflection coating film having athickness of 82 nm. Then, the positive resist composition was appliedonto the antireflection coating film using a spinner, and dried byprebake on a hot plate at 130° C. for 90 seconds to form a resist filmhaving a thickness of 200 nm on the antireflection coating film.

A protective film material, which was obtained by dissolving a mixedresin comprised of DEMNUM S-20 (manufactured by DAIKIN INDUSTRIES, Ltd.)and CYTOP (manufactured by ASAHI GLASS CO., LTD.)(weight ratio=1:5) inperfluorotributylamine to have the resin concentration 2.5 wt %, wasapplied onto the resist film by spin coating, and heated at 90° C. for60 seconds to form a protective film having a thickness of 37 nm.

Subsequently, the resist film was irradiated (exposed) through a maskpattern with pattern light using an ArF excimer laser (wavelength: 193nm) by means of an exposure system NSR-S302B (manufactured by NikonCorporation, NA (numerical aperture)=0.60, ⅔ annular illumination).Then, in a liquid immersion lithography, while rotating the siliconwafer having the resist film exposed, pure water at 23° C. was allowedto fall dropwise against the resist film for 2 minutes. This stepcorresponds to the step in the practical production process in which theresist film completely immersed in the liquid is exposed. However, thestep has a simplified construction such that pure water as a refractiveindex liquid (immersion liquid) is applied to the resist film after theexposure in order to achieve an evaluation of only the effect of theimmersion liquid on the resist film which is previously exposed. This isbecause based on the above-stated analysis on the liquid immersionlithography method, completion of the exposure in the optics istheoretically guaranteed.

After the step of allowing pure water to fall dropwise, the resultantresist film was subjected to PEB treatment under conditions at 130° C.for 90 seconds, and then the protective film was removed usingperfluoro(2-butyltetra-hydrofuran). Then, the resist film was developedusing an alkaline developer solution at 23° C. for 60 seconds. As thealkaline developer solution, a 2.38% by mass aqueous solution oftetramethylammonium hydroxide was used.

Thus obtained resist pattern having a 130 nm line and space of 1:1 wasexamined under a scanning electron microscope (SEM), and, as a result,the pattern profile was found to be excellent such that no fluctuationwas observed at all.

The sensitivity was 17.0 mJ/cm², and the depth of focus was 1.0 μm. Anexposure margin in which a 130 nm line pattern was obtained within ±10%was as excellent as 13.15%.

Example 7

The resin component, acid generator, and nitrogen-containing organiccompound shown below were uniformly dissolved in an organic solvent toprepare a positive resist composition.

As the resin component, a polymer comprising constitutional unitsrepresented by the general formulae (41) and (45) below (85 parts bymass of the units of formula (41) and 15 parts by mass of the units offormula (45)) was used. The resin component had a mass average molecularweight of 10,000.

As the acid generator, 2.4 parts by mass of triphenylsulfoniumnonafluorobutanesulfonate was used.

As the organic solvent, 1,900 parts by mass of a mixed solvent ofpropylene glycol monomethyl ether acetate and ethyl lactate (mass ratio:6:4) was used.

As the nitrogen-containing organic compound, 0.27 part by mass oftriethanolamine was used. As the organic carboxylic acid, 0.26 part bymass of salicylic acid was used.

wherein x=40 mol %, y=40 mol %, and z=20 mol %.

An antireflection coating film, a positive resist using the resistcomposition, and a protective film were formed on a substrate inaccordance with substantially the same procedure as in Example 1 (exceptthat the thickness of the resist film was changed to 150 nm, that theprebake conditions were changed to those at 95° C. for 90 seconds, andthat the PEB conditions were changed to those at 90° C. for 90 seconds).

The substrate having the protective film formed thereon was subjected toimmersion lithography in the same manner as in Example 2.

The resist film was subjected to PEB treatment, and then the protectivefilm was removed under the same conditions as those used in Example 1,and allowed to stand in a place having an amine concentration of about 5ppb in air for 180 seconds, followed by development.

Thus obtained resist pattern having a 130 nm line and space of 1:1 wasexamined under a scanning electron microscope (SEM), and, as a result,the pattern profile was found to be excellent such that no fluctuation(pattern narrowing) was observed. The sensitivity was 26.0 mJ/cm².

Comparative Example 8

The resist composition prepared in Example 7 was allowed to stand for180 seconds in the same manner as in Example 7, and then a resistpattern was formed in substantially the same manner as in Example 7except that no protective film was used.

The resist pattern having a 130 nm line and space of 1:1 was examinedunder a scanning electron microscope (SEM), and, as a result, thepattern profile was found to have a T-TOP form. The sensitivity was 33.0mJ/cm².

The reason for this resides in that no protective film was used andhence amine contained in air deactivated acid on the resist film.

As can be seen from the results of Example 7 and Comparative Example 8,the use of the protective film can prevent the resist film from beingadversely affected by the amine contained in air. That is, the postexposure delay is drastically improved.

Example 8

As component (A), a mixed resin of 85 parts by mass of a silsesquioxaneresin of the chemical formula (46) below and 15 parts by mass of amethacrylate-acrylate copolymer comprising three types of constitutionalunits represented by the chemical formula (47) below was used. In theconstitutional units in the copolymer of the chemical formula (47), v,w, and x are as follows: v=40 mol %, w=40 mol %, and x=20 mol %, and thecopolymer had a mass average molecular weight of 10,000.

As component (B), 2.4 parts by mass of triphenylsulfoniumnonafluorobutanesulfonate was used.

As component (C), 1,900 parts by mass of a mixed solvent of ethyllactate and γ-butyrolactone (mass ratio: 8:2) was used.

As component (D), 0.27 part by mass of triethanolamine was used.

As component (E), 0.26 part by mass of salicylic acid was used.

Next, an organic antireflection coating composition “AR-19” (trade name;manufactured by Shipley Limited) was applied onto a silicon wafer usinga spinner, and dried by calcination on a hot plate at 215° C. for 60seconds to form an organic antireflection coating film having athickness of 82 nm. The positive resist composition was applied onto theantireflection coating film using a spinner, and dried by prebake on ahot plate at 95° C. for 90 seconds to form a resist layer having athickness of 150 nm on the antireflection coating film. Then, the resistfilm was spin-coated with a fluorine protective film material having aresin concentration of 2.5 wt %, which was prepared by dissolving amixed resin of DEMNUM S-10 (manufactured by DAIKIN INDUSTRIES, Ltd.) andCYTOP (manufactured by ASAHI GLASS CO., LTD.)(weight ratio=1:5) inperfluorotributylamine, and heated at 90° C. for 60 seconds to form aprotective film having a thickness of 37 nm.

Then, in the evaluation test 2, using laboratory equipment prepared byNikon Corporation, the resultant resist film was subjected to immersionlithography by 193-nm two-beam interferometry using a prism and water(two-beam interferometry experiment). A similar method is disclosed inthe document 2 (J. Vac. Sci. Technol. B(2001) 19(6), p2353-2356) above,which is known as a method by which a L&S pattern can be easily obtainedin a laboratory scale.

In the immersion lithography in Example 8, a solvent layer of water asan immersion solvent was formed between the top surface of theprotective film and the bottom surface of the prism.

The exposure energy was selected so that the L&S pattern was constantlyobtained. Subsequently, the resist film was subjected to PEB treatmentunder conditions at 90° C. for 90 seconds, and the protective film wasremoved using perfluoro(2-butyltetrahydrofuran). Then, the resist filmwas developed in the same manner as in Example 1 to obtain a 65 nm lineand space (1:1). The pattern form obtained had high squareness.

As described above, in the present invention, even when a resist film isformed using any resist composition commonly used, a resist pattern withhigh resolution can be obtained by a liquid immersion lithographyprocess wherein the resist pattern is advantageous not only in that theresist pattern does not suffer surface roughening, e.g., T-top form andhas high sensitivity and excellent resist pattern profile form, but alsoin that the resist pattern has excellent depth of focus and excellentexposure margin as well as excellent post exposure delay. Therefore, theuse of the protective film according to the present invention makes itpossible to effectively form a resist pattern using the liquid immersionlithography process.

REFERENCES

-   1. Journal of Vacuum Science & Technology B (J. Vac. Sci.    Technol. B) (Published in the United States) 1999, Vol. 17, 6th    edition, pp.3306-3309-   2. Journal of Vacuum Science & Technology B (J. Vac. Sci.    Technol. B) (Published in the United States) 2001, Vol. 19, 6th    edition, pp.2353-2356-   3. Proceedings of SPIE Vol. 4691 (Published in the United States)    2002, Vol. 4691, pp.459-465

1. A material for forming a resist protecting film which is for use in aliquid immersion lithography process and which is formed on a resistfilm, the material having the following properties of: being transparentwith respect to exposure light; having substantially no compatibilitywith a liquid for liquid immersion lithography; and causing no mixingwith the resist film.
 2. The material for forming a resist protectingfilm for use in a liquid immersion lithography process according toclaim 1, wherein the liquid immersion lithography process is of aconstruction in which the resist film is exposed through the liquid forliquid immersion lithography present at least on the resist film in apath of the lithography exposure light toward the resist film, whereinthe liquid has a predetermined thickness and has a refractive indexlarger than that of air and smaller than that of the resist film,whereby improving the resolution of a resist pattern.
 3. The materialfor forming a resist protecting film for use in a liquid immersionlithography process according to claim 1, wherein the liquid for liquidimmersion lithography is water substantially comprised of pure water ordeionized water.
 4. The material for forming a resist protecting filmfor use in a liquid immersion lithography process according to claim 1,wherein the resist film is formed from a resist composition comprised ofa base polymer which is a polymer comprising (meth)acrylic ester units.5. The material for forming a resist protecting film for use in a liquidimmersion lithography process according to claim 1, wherein the resistfilm is formed from a resist composition comprised of a base polymerwhich is a polymer having dicarboxylic acid anhydride-containingconstitutional units.
 6. The material for forming a resist protectingfilm for use in a liquid immersion lithography process according toclaim 1, wherein the resist film is formed from a resist compositioncomprised of a base polymer which is a polymer having phenolic hydroxylgroup-containing constitutional units.
 7. The material for forming aresist protecting film for use in a liquid immersion lithography processaccording to claim 1, wherein the resist film is formed from a resistcomposition comprised of a base polymer which is a silsesquioxane resin.8. The material for forming a resist protecting film for use in a liquidimmersion lithography process according to claim 1, wherein the resistfilm is formed from a resist composition comprised of a base polymerwhich is a polymer having α-(hydroxyalkyl)acrylic acid units.
 9. Thematerial for forming a resist protecting film for use in a liquidimmersion lithography process according to claim 1, wherein the resistfilm is formed from a resist composition comprised of a base polymerwhich is a polymer having dicarboxylic acid monoester units.
 10. Thematerial for forming a resist protecting film for use in a liquidimmersion lithography process according to claim 1, which has thefollowing properties: having substantially no compatibility with purewater or deionized water; and causing no mixing with the resist film.11. The material for forming a resist protecting film for use in aliquid immersion lithography process according to claim 1, which is acomposition comprising at least a fluorine-substituted polymer.
 12. Thematerial for forming a resist protecting film for use in a liquidimmersion lithography process according to claim 11, wherein thefluorine-substituted polymer is comprised of any one of cyclicperfluoroalkyl polyether and chain perfluoroalkyl polyether or both. 13.The material for forming a resist protecting film for use in a liquidimmersion lithography process according to claim 12, wherein thecomposition is obtained by dissolving any one of the cyclicperfluoroalkyl polyether and the chain perfluoroalkyl polyether or bothin a fluorine solvent.
 14. A composite film for use in a liquidimmersion lithography process, the composite film comprising aprotective film and a resist film, wherein the protective film has thefollowing properties: being transparent with respect to exposure light;having substantially no compatibility with a liquid for liquid immersionlithography; and causing no mixing with the resist film, and wherein theprotective film is formed on the resist film.
 15. The composite film forliquid immersion lithography process according to claim 14, wherein theliquid immersion lithography process is of a construction in which thecomposite film is exposed through the liquid for liquid immersionlithography present at least on the resist film in a path of thelithography exposure light toward the resist film, wherein the liquidhas a predetermined thickness and has a refractive index larger thanthat of air and smaller than that of the resist film, thus improving theresolution of a resist pattern.
 16. The composite film for liquidimmersion lithography process according to claim 14, wherein the liquidfor liquid immersion lithography is water substantially comprised ofpure water or deionized water.
 17. The composite film for liquidimmersion lithography process according to claim 14, wherein theprotective film has the following properties: having no compatibilitywith pure water or deionized water; and causing no chemical mixing withthe resist film.
 18. The composite film for liquid immersion lithographyprocess according to claim 14, wherein the protective film is a coatingfilm of a composition comprising at least a fluorine-substitutedpolymer.
 19. The composite film for liquid immersion lithography processaccording to claim 18, wherein the fluorine-substituted polymer iscomprised of any one of cyclic perfluoroalkyl polyether and chainperfluoroalkyl polyether or both.
 20. The composite film for liquidimmersion lithography process according to claim 19, wherein thecomposition is obtained by dissolving any one of the cyclicperfluoroalkyl polyether and the chain perfluoroalkyl polyether or bothin a fluorine solvent.
 21. The composite film for liquid immersionlithography process according to claim 14, wherein the resist film isformed from a resist composition comprised of a base polymer which is apolymer comprising (meth)acrylic ester units.
 22. The composite film forliquid immersion lithography process according to claim 14, wherein theresist film is formed from a resist composition comprised of a basepolymer which is a polymer having dicarboxylic acid anhydride-containingconstitutional units.
 23. The composite film for liquid immersionlithography process according to claim 14, wherein the resist film isformed from a resist composition comprised of a base polymer which is apolymer having phenolic hydroxyl group-containing constitutional units.24. The composite film for liquid immersion lithography processaccording to claim 14, wherein the resist film is formed from a resistcomposition comprised of a base polymer which is a silsesquioxane resin.25. The composite film for liquid immersion lithography processaccording to claim 14, wherein the resist film is formed from a resistcomposition comprised of a base polymer which is a polymer havingα-(hydroxyalkyl)acrylic acid units.
 26. The composite film for liquidimmersion lithography process according to claim 14, wherein the resistfilm is formed from a resist composition comprised of a base polymerwhich is a polymer having dicarboxylic acid monoester units.
 27. Amethod for forming a resist pattern using a liquid immersion lithographyprocess, the method comprising: forming a photoresist film on asubstrate; forming, on the resist film, a protective film having thefollowing properties of: being transparent with respect to exposurelight, having substantially no compatibility with a liquid for liquidimmersion lithography, and causing no mixing with the resist film;directly placing the liquid for liquid immersion lithography having apredetermined thickness at least on the protective film on the substratehaving the resist film and the protective film stacked thereon;selectively irradiating the resist film with light through the liquidfor liquid immersion lithography and the protective film, and optionallysubjecting the resultant resist film to heat treatment; removing theprotective film from the resist film irradiated; and developing theresist film from which the protective film is removed to obtain a resistpattern.
 28. The method for forming a resist pattern according to claim27, wherein the liquid immersion lithography process is of aconstruction in which the resist film is exposed through the liquid forliquid immersion lithography present at least on the resist film in aray of the lithography exposure light toward the resist film, whereinthe liquid has a predetermined thickness and has a refractive indexlarger than that of air and smaller than that of the resist film,whereby improving the resolution of a resist pattern.